US9735449B2 - Electrolyte composition - Google Patents

Electrolyte composition Download PDF

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US9735449B2
US9735449B2 US14/672,738 US201514672738A US9735449B2 US 9735449 B2 US9735449 B2 US 9735449B2 US 201514672738 A US201514672738 A US 201514672738A US 9735449 B2 US9735449 B2 US 9735449B2
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electrolyte composition
graphene
battery
present
electrolyte
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US20150280286A1 (en
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Ting-Yuan Wu
Yu-Wei Chang
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Eternal Materials Co Ltd
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Eternal Materials Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators
    • H01M10/08—Selection of materials as electrolytes
    • C01B31/0438—
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0005—Acid electrolytes
    • H01M2300/0011—Sulfuric acid-based
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a novel electrolyte composition and a battery, particularly a novel graphene-containing electrolyte composition useful for a battery.
  • batteries can be divided into chemical batteries and physical batteries, and chemical batteries can further be divided into primary batteries, secondary batteries and fuel batteries.
  • Secondary batteries also known as rechargeable batteries, are charged/recharged by applying an electric current, which reverses the chemical reactions that occur during discharge/use.
  • Common secondary batteries include nickel metal hydride battery (NiMH battery or nickel hydride battery), lead-acid battery and lithium ion battery.
  • NiMH battery or nickel hydride battery nickel metal hydride battery
  • lead-acid battery lithium ion battery.
  • the lead-acid battery though the oldest form of secondary batteries, still remains popular for its good reliability, low cost for manufacture and purchase, and high regeneration rate.
  • a conventional lead-acid battery comprises a negative electrode of metallic lead, a positive electrode of lead dioxide, and a diluent sulfuric acid electrolyte.
  • the chemical reactions during battery discharge are indicated below:
  • the lead sulfate formed on the electrodes cannot be completely converted to lead ions and sulfate ions during the recharge cycles, and therefore the amount of the sulfate ions in the electrolyte will gradually decrease.
  • This problem would become more severe when a coarse lead sulfate cluster forms due to deep discharge or rapid recharge of the battery.
  • the residual lead sulfate degrades the cooling rate of the electrodes and reduces the effective surface area of the Pb and PbO 2 electrodes, thereby reducing the capacity and life cycle of the battery.
  • Another problem is water loss due to gas evolution, which happens when the water contained in an electrolyte solution is electrolyzed during deep discharge or rapid recharge/charge of the battery or is evaporated due to heat accumulated in the battery.
  • the water loss makes it harder to dissolve lead sulfate; the oxygen and hydrogen produced during the electrolysis of water jeopardizes the safety of the battery. Furthermore, the presence of sulfuric acid concentration gradient increases the internal resistance of the battery, decreases the mobility of the ions, and thus adversely affects the performance of the battery.
  • CN 102201575 discloses a lead sulfate-graphene composite electrode material and a negative paste comprising the same
  • CN 101719563 discloses a lead-acid battery with graphene added to the negative electrode
  • US 20120328940 A1 discloses the use of carbon nanotubes or graphene as an additive in the electrodes
  • CN 1505186 and US 2005181282 disclose use of carbon nanotubes for the cathode and anode of lead-acid batteries. It is believed that using carbon nanotubes and/or graphene in the electrodes can improve the properties of the lead-acid battery.
  • the present invention provides an electrolyte composition and a battery to solve the above problems.
  • the present invention provides a battery comprising the electrolyte composition.
  • the present invention can effectively improve the performance of a battery.
  • FIG. 1 shows capacity change measured after charge/discharge cycles for the unit cells using a conventional electrolyte composition and the electrolyte composition according to the present invention.
  • FIG. 2 shows SEM images of the positive and negative electrodes of the unit cells using a conventional electrolyte composition and the electrolyte composition according to the present invention.
  • FIG. 3 shows capacity change measured after charge/discharge cycles for the unit cells in which an electrolyte composition with a different concentration of graphene was used.
  • the word “about” is used to describe and account for an acceptable deviation for a certain value measured by a person of ordinary skill in the art.
  • the range of the deviation depends on how the value is measured.
  • the present invention provides a graphene-containing electrolyte composition.
  • Graphene is a 2-dimensional, crystalline allotrope of carbon. In graphene, carbon atoms are densely packed in a regular sp 2 -bonded hexagonal pattern. Graphene includes single-layer graphene and multilayer graphene. Single-layer graphene refers to a sheet of one atomic layer of carbon molecules having ⁇ bonds.
  • the inventors of the present invention found that the performance of a battery, especially a lead-acid battery, can be effectively enhanced by adding graphene to an electrolyte composition of the battery.
  • graphene has superior thermal conductivity, electric conductivity and specific surface area and is more soluble in an aqueous solution and suitable for large-scale production.
  • the inventors of the present invention further found that when applied to an electrolyte composition, the superior thermal conductivity and electric conductivity of graphene can effectively reduce the water loss due to gas evolution during the operation of a battery, which results in improved performance of a battery.
  • the sulfuric acid concentration gradient can be effectively reduced by adding graphene to an electrolyte composition, thereby increasing the mobility of sulfate ions, decreasing the internal resistance due to the sulfuric acid concentration gradient and enhancing the battery performance; the high specific surface area of graphene and the decrease of the sulfuric acid concentration gradient decrease the size of the lead sulfate cluster formed on the electrodes of lead-acid battery and thus can improve the properties of the electrodes.
  • the present invention provides an electrolyte composition
  • an electrolyte composition comprising (1) water, (2) sulfuric acid and (3) graphene.
  • the graphene is present in an amount of about 0.001 to about 1 wt %, preferably about 0.003 to about 0.2 wt %, most preferably about 0.005 to about 0.1 wt %, based on the total weight of the electrolyte composition.
  • An excessive amount of graphene (for example, >1 wt %) may cause a short circuit.
  • the electrolyte composition of the present invention has a specific gravity from about 1.12 to about 1.28.
  • the amount of sulfuric acid in the electrolyte composition is not particularly limited and can be any suitable amount known to a person of ordinary skill in the art or adjusted by a person of ordinary skill in the art as needed.
  • the sulfuric acid is present in an amount of about 10 to about 75 wt %, preferably about 12 to about 45 wt %, most preferably about 15 to about 40 wt %, based on the total weight of the electrolyte composition.
  • a conventional electrolyte composition usually has a resistance over 600 ⁇ while the electrolyte composition of the present invention has a resistance of no greater than 600 ⁇ .
  • the decrease of resistance can improve the capacity efficiency during deep discharge or rapid recharge/charge of the battery, and thus can enhance battery performance.
  • the preferable resistance is in the range of 100 to 600 ⁇
  • the graphene useful to the present invention can be prepared through any suitable process, for example, the conventional processes including mechanical exfoliation, epitaxial growth, chemical vapor deposition (CVD), liquid phase exfoliation and high temperature furnace carbonization.
  • the conventional processes including mechanical exfoliation, epitaxial growth, chemical vapor deposition (CVD), liquid phase exfoliation and high temperature furnace carbonization.
  • CVD chemical vapor deposition
  • liquid-phase exfoliation of bulk graphite is considered an up-scalable approach to obtain high-quality single layer graphene with equipment available in chemistry labs.
  • the graphene of the present invention is a thin graphene flake or sheet. If the graphene size is too large, graphene may precipitate due to insufficient buoyant force, which may cause a partial short circuit.
  • the graphene of the present invention has a lateral dimension from about 20 nm to about 1 ⁇ M and a thickness from about 0.35 nm to about 10 nm.
  • the graphene useful to the present invention is modified with functional groups, to improve the properties of the graphene.
  • the graphene can be optionally modified with hydrophilic groups so as to provide an improved dispersibility, which prevents graphene from precipitating, aggregating, or suspending at the surface of the electrolyte, and prevents the demixing of the electrolyte composition.
  • hydrophilic groups include, but are not limited to, hydroxyl group (—OH), amino group (—NH 2 ), carboxyl group, carbonyl group and phosphate group.
  • the graphene useful to the present invention is modified with a hydroxyl group (—OH) or an amino group (—NH 2 ).
  • the modified graphene useful to the present application can be prepared by any suitable process, including but not limited to liquid-phase exfoliation.
  • the modified graphene useful to the present application has a carbon content of more than about 80 mol % and an oxygen content from about 1 mol % to about 20 mol %. If the carbon content is too low (e.g., less than about 80 mol %), conductivity may decrease. If the oxygen content is too low (e.g., less than about 1 mol %), the wettability of modified graphene is worse and the conductivity may decrease. If the oxygen content is too high (e.g., more than about 20 mol %), the conductivity may decrease.
  • the electrolyte composition of the present invention can optionally comprise any suitable additives that are known to a person of ordinary skill in the art, for example, those added to an electrolyte composition to improve the disadvantages, such as high internal resistance, low capacity or demixing of the electrolyte composition, or those added to increase battery life.
  • additives commonly used in the art include, but are not limited to, sulfates containing alkali metal or alkaline earth metal, phosphoric acid, cobalt sulfate, cadmium sulfate, tin sulfate, copper sulfate, zinc sulfate, nickel sulfate, aluminum sulfate, sodium carbonate, potassium hydroxide or sodium hydroxide, fumed silica, or silica (silicon dioxide).
  • Adding sodium carbonate, potassium hydroxide, sodium hydroxide or silicon dioxide to the electrolyte composition is beneficial for maintaining the uniformity of the sulfuric acid concentration, reducing polarization, enhancing the sustainability of the graphene and increasing battery life for a lead-acid battery; silicon dioxide is preferred.
  • the amount of the additives is not particularly limited and can be adjusted by a person of ordinary skill in the art as needed. In an embodiment of the present invention, the amount of the additives can be about 0.01 to about 10 wt %, preferably about 0.1 to about 5 wt %, based on the total weight of the electrolyte composition.
  • the electrolyte composition of the present invention can be applied to any suitable field.
  • the electrolyte composition of the present invention is used in a battery, preferably in a lead-acid battery.
  • the present invention further provides a battery comprising the above electrolyte composition, which can be, but is not limited to, a nickel hydride battery, lead-acid battery, lithium ion battery or dye-sensitized solar cell.
  • a battery comprising the above electrolyte composition, which can be, but is not limited to, a nickel hydride battery, lead-acid battery, lithium ion battery or dye-sensitized solar cell.
  • the present invention provides one or more of the following advantages:
  • the electrolyte composition of the present invention comprises a electrolyte composition containing graphene. Due to the above advantages (2) and (3), the surface temperature of the unit cell in which an electrolyte composition of the present invention is used would be lower (for example, about 2-5° C.) than that of the unit cell in which a traditional electrolyte (i.e., without graphene) is used, after a lot of charge/discharge cycles. In addition, the temperature difference between the electrolyte solution and the electrode of the latter unit cell is greater than that of the former unit cell. Thus, the electrolyte composition containing graphene can improve the overheating of the battery and prevents the electrodes from deterioration.
  • the unit cells were subjected to a charge/discharge cycling test. Each of the unit cells was rapidly charged at a ratio of 0.2 C (i.e., 800 mA/hour) to 95% or above of its rated capacity and then discharged at a rate of 0.2 C to 80% DOD (depth of discharge). The capacity (%) of the unit cells was measured after each cycle and the results are shown in FIG. 1 .
  • the term “DOD (depth of discharge)” in the present invention refers to the ratio of the capacity removed from a cell during discharge to the rated capacity of the cell. The capacity of a cell will be reduced after repeated charged and discharged; in general, the cell is “dead” when its capacity is lower than 50%.
  • the positive and negative electrodes of the two unit cells in Example 1 were observed with a scanning electron microscope (SEM; Hitachi S-3400N) after 30 charge/discharge cycles. The results are shown in FIG. 2 .
  • FIG. 2 (a) and (b) respectively show images of the positive and negative electrodes of the unit cell containing a traditional electrolyte solution (“Electrolyte”; no graphene); (c) and (d) respectively show images of the positive and negative electrodes of the unit cell containing an electrolyte solution of the present invention (“Graphenetrolyte”; with graphene).
  • the carbon content was measured by EDAX (Energy Dispersive Analysis of X-rays); the results show that the carbon contents in (a) and (b) are zero and the carbon contents in (c) and (d) are 8.6 mol % and 3.4 mol %, respectively.
  • graphene in the electrolyte composition of the present invention was adsorbed on the surface of the positive and negative electrodes and thus graphene-containing electrodes were formed.
  • FIGS. 2 (a) and (b) sulfates were adsorbed on the surface of the positive and negative electrodes of the unit cell in which a traditional electrolyte solution was used. Comparing FIGS. 2 (c) and (d) with FIGS. 2 (a) and (b), it can be seen that graphene is adsorbed on the positive and negative electrodes when the electrolyte composition of the present invention is used, which suppresses the growth of large lead sulfate crystals on the positive and negative electrodes and increases the thermal conduction efficiency of the electrodes, effectively increasing the life cycle of the lead-acid battery.
  • the electrolyte solutions containing graphene (“50 ppm Graphenetrolyte,” “150 ppm Graphenetrolyte” and “500 ppm Graphenetrolyte”) notably increased the life cycle of the unit cells.

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  • Condensed Matter Physics & Semiconductors (AREA)
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